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ESR studies of intramolecular electron transfer in malonic acid radical chelates of cerium(IV)

Brusa, M. A. and Perissinotti, L. J. and Colussi, A. J. (1988) ESR studies of intramolecular electron transfer in malonic acid radical chelates of cerium(IV). Inorganic Chemistry, 27 (24). pp. 4474-4477. ISSN 0020-1669. http://resolver.caltech.edu/CaltechAUTHORS:20150623-154809318

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Abstract

The reduction of Ce(IV) complexed to dicarboxymethyl (malonic acid radical; •CH(COOH),) has been directly investigated by kinetic electron spin resonance spectrometry in aqueous perchloric acid media at 298 K. The corresponding first-order rate constant has a value of k_(11) = (1.5 ± 0.3) x10^3 s^(-1). Free (M_1) and Ce(IV)-chelated (M_2) dicarboxymethyl radicals have slightly different magnetic parameters [g(M_1) = 2.0039, a(H_α)(M_1) = 20.3 G, g(M_2) = 2.0035, a(H_α)(M_2) = 19.6 G] and coexist in equilibrium, the ratio r = [M_2]/[M_1] being a function of both [Ce(IV)] and [H^+]. The stability constant of the radical chelate, K_g = 242 ± 31 M^(-1), is considerably larger than that of malonic acid itself, K_5 = 1.14 M^(-1). The product K_gk_(11), which represents the overall rate constant for dicarboxymethyl radical oxidation by Ce(IV), has a value within the range of those measured for the direct oxidations of substituted secondary alkyl radicals by Ce(IV), Co(III), and Ti(IV).


Item Type:Article
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URLURL TypeDescription
http://dx.doi.org/10.1021/ic00297a027DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic00297a027PublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1988 American Chemical Society. Received January 5, 1988.
Record Number:CaltechAUTHORS:20150623-154809318
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150623-154809318
Official Citation:ESR studies of intramolecular electron transfer in malonic acid radical chelates of cerium(IV) M. A. Brusa, L. J. Perissinotti, and A. J. Colussi Inorganic Chemistry 1988 27 (24), 4474-4477 DOI: 10.1021/ic00297a027
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58526
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:24 Jun 2015 22:25
Last Modified:24 Jun 2015 22:25

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